2, 2&#39;-(2, 5-lower dialkoxy-p-phenylene)-di-(anthra[2, 1]thiazole-6, 11-diones)



Patented Sept. 15, 1953 um rso SE'IZATES 2,2'- (2,5-LOWER DIALKOXYm-PHENYL'ENE') DI- (ANTHRAT2,1]THIAZOLE- GJI-DIONE 3')" Nicholas Easton, Pa. assignors Film Gorporation, New York, .N.=Y., a-corporationofDelaware' w. Solonen and Davida Randall to General Aniline &.-

No Di-awingr... Application December 711951, l Serial No. 260,583

1. This invention relates -towatdyestuffs and particularly to 2,2"-(2;5.-1ower dialkoxy-p-phenylene) -di-(anthra[2,1] -thiazo1e -6,11-diones) It is an object of. the present invention to provide 2,2"-(2,5..-lower dialkoxy p-phenylene)-di- (anthra ['2,1]thiazole-6,1l-diones) whichare use-- ful as vat dyes having exceptional brightness in color and fastness to fabrics.

Other objects and advantages will be apparent from the following specification in which the preferred details and. embodiments .are described.

The vat dyes of this' invention are characterized 1 by azstructure;corresponding;to the. general formula: 1 i

wherein-Rrepresents alowerallyl group; e: gr,

methyl, ethyl, propylj isopropyl; butylj isobutyl;

etc. i

The vatdyes illustrated by the foregoing formula are obtained in good yields' by first reacting a molecular equivalent of a 2,5-lower dialk'oxyterephthalic acidwith two molecularequivalents oi thionyl chloride in the presence of anhydrous o-dichlorobenzeneata temperature-ranging from Z-amino-lschloroanthraquinonein: a mixture:

consisting of about 40- partsaoftanhydrous oadi chlorobenzene and. 1 .part .ofspyridinen The-acids chloride solution is then heated atu1.10l-ito-1l59 for 7 hours, cooled to room temperature and the product, 2,5-lower dialkoxyterephthaloyl-di-(2- amido-l-chloroanthraquinone) filtered, washed wtih anhydrous o-dichlorobenzene, ethanol, and water, and finally dried.

A molecular equivalent of the above product is added to a mixture consisting of about 161' parts of pyridine, '7 parts of sodium sulfide andi part' of sulfur. The resulting mixture is heated to about 6 Claims; (Cl. 260-303) -to C. and maintainedrat-this.temperature for about? to.-.8:"hours.: After cooling to-roomtemperature; the: product,

dried.

A molecular equivalent of.- the mercapto. derivative is slowly addedtoatsolution .consistingofl. about 18=parts of 196% sulfuricacidiand. l-ipart. of waterpthe solution 'heated to. about 105. Ova-rick maintained atz this. temperature: with .stirring -.fort

about 2 to 3 hours. The reaction mixture is cooled to room temperature; poured-.-over ice and water mixture, and the resultin precipitate allowed to stand overnight. The: final product is then filtered, washed neutral with water, and dried. All of the parts given-above are by weight.

As examples of suitable-2,5 lower dialkoxyterephthalicxacids, the following may be mentioned:

2,5-dimethoxyterephtha1icr acid 2,5-diethoxyterephthalic acid,- 2,5 -dipropoxyterephthalic acid 2,5'-dibutoxyterephthalic acid The following "examples: describe the'preparation of some of the 2,2-(2,5lower dialkoxy-pphenylene) -di= (anthra [2,1] thiazole 6,11-.-- di ones). All partseiven-amrby weight,-

Eitample I (l ona i G t l as, N

u |1 O O [22-(2,5rdimethoxy-p-phenylene)-cli-(anthra[2,1]

thiazole-G,1 ll-di'oneyfl 15+ parts of 2,5-dimethoxyterephtlia1ici acid were-added 110.140 parts of anhydrous o dichlorobenzene followed by the addition of20 parts of thionyl chloride, and the resulting mixture gradually brought up to .140? C. The reactionwas maintainedat' this temperaturefr' 3hours with eificient stirring. At the end of this time, the excess thionyl ichlori'de :was distilled out byipass ing in dry.- airvatr1509 .andithei original volumei of thefireaction mixturafrestoredrby the -addition"; of canhydroussoedichlorobenzene. The acid sch-10a rider: solution: was filteredand added slowly to a l solution of. 31:2, arts of; Zeamiizo bohldro ii anthraquinone 2 inn TQQrpa-rts of I; anhydrmisi mdie 235"- dialkoxyteree phthaloyl-di-(Z amide-"1-mercapto-anthraquin-s one), is steam. distilled, filtered. Washed and chlorobenzene and 20 parts of pyridine while the latter was at 110 to 115 C. After the addition of the acid chloride solution was complete, the reaction mixture was maintained at 110 to 115 C. for '7 hours. After cooling to room temperature, the product was filtered, the presscake washed with anhydrous o-dichlorobenzene, ethanol, and water, and then dried.

40 parts of the above product, 2,5-dimethoxyterephthaloyl di (2 amido-l chloroanthraquinone), were added to a mixture of 216 parts of pyridine, 87 parts of crystalline sodium sulfide and 12 parts of sulfur. The resulting mixture was brought up to 90 C. and maintained at that temperature for about '7 hours. After cooling to room temperature, the product was filtered and the moist presscake steam distilled. The mercapto-derivative was then filtered, washed with water, and dried.

30 parts of 2,5-dimethoxyterephthaloyl-di-(2- 'amido-l-mercaptoanthraquinone), prepared as above, were slowly added to a sulfuric acid solution composed of 945 parts of 96% sulfuric acid and 52 parts of water. The resulting solution was gradually brought up to 105 C. and maintained at this temperature with stirring for about 2 hours. The reaction was cooled to room temperature and poured into 9550 parts of a mixture of ice and water. After allowing the precipitate to stand overnight, it was filtered, washed neutral with water, and dried.

Example II I N O 0 [2,2- (2,5-diethoxy-p-phenylene)rdi- (anthra [2,1] thiazole-6,11-dione) Example III [2,2- (2,5-dibutoxy-p-pheny1ene)-di (anthra [2,1] -thiazo1e- 6,11-dione) Example I was repeated with the exception that parts of 2,5-dimethoxyterephthalic acid were replaced by 20.5 parts of 2,5-dibutoxyterephthalic acid in the initial reaction step. The subsequent reaction steps were conducted by utilizing the appropriate molecular equivalent proportions of the coreactants.

4 Example IV (i'l) S -C O S (I? [2,2'-(2,E-dipropoxy-p-phenylene)-di- (anthra [2,1] thiazole-6,11-dione) Example I was repeated with the exception that 15 parts of 2,5-dimethoxyterephthalic acid were replaced by 18.? parts of 2,5-dipropoxy- [2,2'- (2,5-diisopropoxy-p-phenylene) -di- (anthra [2,1]

thiazo1e-6,11-dione) Example I was repeated with the exception that 15 parts of 2,S-dimethoxyterephthalic acid were replaced by 18.! parts of 2,5-diisopropoxyterephthalic acid in the initial reaction step. The subsequent reaction steps were conducted by utilizing the appropriate molecular equivalent proportions of the coreactants.

All of the foregoing vat dyestuffs have great afiinity for textile fabrics, have a strong orange shade and remain fast when applied to fabrics, particularly cotton. While there have been pointed out certain preferred embodiments of the invention, the same is not limited to the foregoing examples or to the specific details given therein, but are capable of variation and modification as to the reactants, proportions, and conditions employed.

We claim:

1. 2,2 (2,5 lower dialkoxy-p-phenylene) -61- (anthra[2,llthiazole-6,l1-diones) characterized by the following general formula:

---o- -o--s (anthra[2,1l thiazole 6,1l-dione)l having the following formula:

6 3. [2,2' (2,5 diethoxy p pheny1ene)-di- 6. [2,2' (2,5 diisopropoxy p phenylene- (anthra[2,1]-thiazole-6,11-dione)J having the di-(anthra[2,1l-thiazole-6,11-dione)l having the following formula: following formula:

5 0 s-oos 0 0 so-o -s o 1 "u 0" "ul 1;" -N 002115 N N 0011mm N l0 1 (l l 4% 4. [2,2' (2,5 dibutoxy p phenylene) di- NICHOLAS W. SOLONEN. (anthra[2,1] -thiazole-6,11-dione) having the DAVID I. RANDALL. following formula: L 4 OCH References Cited in the file of this patent I UNITED STATES PATENTS T f Number Name Date H a) H 1,459,536 Kacer June 19, 1923 N 01211 N- FOREIGN PATENTS Number Country Date H 101,169 Switzerland Sept. 1, 1923 0 O 204,249 Great Britain Sept. 27, 1923 5. [2,2 (2,5 dipropoxy p phenylene) di- 384,674 Germany Nov. 8, 1923 -thiaZOle-6,11-di0ne)] having the followmg formula:

Georgxevms, Dye chemlstry, Scott, Green- OCBHY wood and Son, London, 1920. I W if? 1 

1. 2,2'' - (2,5 - LOWER DIALKOXY-P-PHENYLENE) -DI(ANTHRA(2,1)THIAZOLE-6,11-DIONES) CHARACTERIZED BY THE FOLLOWING GENERAL FORMULA: 